N-acyl-1 2-dicarbonyl-phenyl-hydrazones

ABSTRACT

N-ACYL-1,2-DICARBONYL-PHENYL-HYDRAZONES, I.E. (A-CYANOA-ALKANOYL AND CARBOALKOXY)-CARBONYL-N-(ALKANOYL, CHLOROALKANOYL, ALKENOYL AND BENZOYL)-((MONO, AND SAME AND MIXED DI AND TRI, -CHLORO AND -TRIFLUOROMETHYL)-PHENYL)HYDRAZONES, WHICH POSSESS ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES.

United States Patent afice 3,631,091 Patented Dec. 28, 1971 US. Cl.260-465 D 10 Claims ABSTRACT OF THE DISCLOSUREN-acyl-1,2-dicarbonyl-phenyl-hydrazones, i.e. (or-cyanoa-alkanoyl andcarboalkoxy)-carbonyl-N-(alkanoyl, chloroalkanoyl, alkenoyl andbenzoyl)-[ (mono, and same and mixed di and tri, -chloro and-trifluoromethyl)-phenyl]- hydrazones, which possess arthropodicidal,especially acaricidal and insecticidal, properties.

The present invention relates to and has for its objects the provisionfor particular new N-acyl-1,2-dicarbonylphenyl-hydrazones, i.e.(a-cyano-oc-alkanoyl and carboalkoxy)-carbonyl-N-(alkanoyl,chloroalkanoyl, alkenoyl and benzoyl) -[(mono, and same and mixed di andtri, -chloro and -trifiuoromethyl)-phenyl]-hydrazones, which possessarthropodicidal, especially insecticidal and acaricidal, properties,active compositions in the form of mixtures of such compounds with solidand liquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new Way especially forcombating pests, e.g. arthropods, With other and further objectsbecoming apparent from a study of the within specification andaccompanying examples.

It is known that certain phenylhydrazones which are derived from malonicdinitrile, such as a,a-dicyano-carbonyl-(3,4-di-chloro-phenyl)-hydrazone (A), can be used for the controlof insects (see US. Pat. 157,569).

It has now been found, in accordance with the present invention, thatthe particular new N-acyl-l,2-dicarbonylphenyl-hydrazones of the formulain which:

X is cyano,

Y is alkyl of 1-4 carbon atoms or alkoxy of 1-4 carbon atoms,

m is a whole integer from 1-3,

Z, each individually, is chloro r trifluoromethyl, and

A is alkyl of 1-4 carbon atoms, chloro-substituted alkyl of 1-4 carbonatoms, alkenyl of 3-4 carbon atoms, or phenyl,

exhibit strong arthropodicidal, especially insecticidal and acaricidal,properties.

It has been furthermore found, in accordance with the present invention,that a process for the production of the compounds of Formula I abovemay now be provided which comprises (a) reacting an alkali metal salt of1,2-dicarb0nylphenyl-hydrazone of the formula in which X, Y, Z and m arethe same as defined above, and Alk is a sodium or potassium cation,

optionally in the presence of a polar solvent, with an acid chloridecompound of the formula 01 (III) in which A is the same as definedabove, or

(b) reacting a l,2-dicarbonyl-phenyl-hydrazone of the formula in whichX, Y, Z and m are the same as defined above, with an acid chloridecompound of Formula III above, preferably in a polar solvent, in thepresence of an approximate equivalent amount of an acid binding agent.

Advantageously, the particular new compounds of Formula I above aredistinguished by outstanding insecticidal and acaricidal properties aswell as, in some cases, extremely low toxicity to warm-blooded animalsand concomitantly low phytotoxicity. It is decidedly surprising that thephenylhydrazones according to the present invention exhibit a stronginsecticidal and acaricidal effectiveness than the chemically verysimilar, previously known phenylhydrazones such as a,a-dicyano-carbonyl-(3,4-dichloro-phenyl)-hydrazone (A). Therefore, the new compounds of thepresent invention represent a valuable enrichment of the art.

It for example the potassium salt ofcyano-carbomethoxy-carbonyl-(3,5-bis trifluoromethyl phenyl)-hydrazoneand propionic acid chloride are used as starting materials, the reactioncourse according to process variant (a) may be illustrated by thefollowing formula scheme:

Subscript represents number of times active compound sequentiallyappears in specification.

The reaction course according to process variant (b) proceeds inanalogous manner.

Advantageously, in accordance with the present inven tion, in thevarious formulae herein:

X represents cyano; Y represents straight and branched chain lower alkylhydrocarbon of 1-4 carbon atoms such as methyl, ethyl, n-, andiso-propyl, n-, iso-, sec.- and tert.-butyl, and the like, especially Cor C alkyl; or

straight and branched chain lower alkoxy of 1-4 car- I bon atoms such asmethoxy, ethoxy, nand iso-propoxy, n-, iso-, sec.- and tert.-butoxy, andthe like, especially C or C alkoxy; 111 represents a whole integer from1 to 3, especially 2-3; Z, each individually, represents chloro;trifluoromethyl; or mixtures thereof;

such that Z on the phenyl ring represents 2-, 3- and 4- mono chloroortrifluoromethyl, -phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-di (sameor mixed) chloroand/ or trifiuoromethyl, and -phenyl, and 2,3,4-,2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- and 3,4,5-tri (same or mixed) chloro and/or trifluoromethyl, -phenyl, especially 3,5-bis-trifiuoromethyl-phenyl,2,4,5-trichloro-phenyl, 2-chloro-5-trifiuoromethyl-phenyl,2-trifluoromethyl-4-chlorophenyl, and the like; and

A represents straight and branched chain lower alkyl hydrocarbon of 1-4carbon atoms such as methyl to tert.-butyl inclusive as defined above,and the like, especially C1 3 r C1 2 chloro-substituted lower alkyl of1-4 carbon atoms such as mono and di-chloro-substituted methyl to tert.-butyl inclusive as defined above, and the like, especially mono-chloro-Cor C or C alkyl and di-chloro-C or C or C alkyl, and more especiallyw-mono and di chloro-C or C or C alkyl;

straight and branched chain lower alkenyl hydrocarbon of 3-4 carbonatoms such as 04-, 5- and -allyl (i.e. prop-1 and 2-enyl, andl-methyl-vinyl), but -l,2 and 3-enyl, 2-methyl-prop-l and 2-enyl, andthe like, especially l-methyl-vinyl and Z-methyl-prop-l-enyl; or phenyl.

Preferably, X is cyano; Y is C or C or C alkoxy; m is 2-3; Z is chloro,trifiuoromethyl, or mixtures thereof; and A is C o1 C alkyl, or phenyl.

The starting alkali metal salts of the phenyl-hydrazones of Formula IVabove can be prepared in simple manner by stirring together oneequivalent of the corresponding hydrazone (IV) with one equivalent ofpotassium or sodium hydroxide in ethanol at 2040 C. and concentratingthe reaction product until crystallization. The salt obtained isexpediently dried at a high temperature. According to another method ofpreparation, one equivalent of such hydrazone (IV) is dissolved inbenzene, one equivalent of sodium or potassium alcoholate is added, andheating to the boil is effected, whereupon the alcohol formed isdistilled off azeotropically. The solid alkali metal salt is obtained byconcentration, or the benzene solution or suspension of the alkali metalsalt is used directly for further reaction.

For the preparation of the corresponding phenylhydrazones (IV),expediently an appropriately substituted diazotized amine is reactedwith suitable active methylene compounds at a temperature from -20 to+30 C. and at a pH value of, preferably, 4 to 8, optionally in a solventsuch as water or alcohol; an acid binding agent such as sodium acetateor sodium carbonate expediently being added to bind the acid which isformed (see US patent application Ser. No. 762,155).

The phenyl-hydrazones of the Formula (IV) can, however, also be preparedby using, in the same manner as above, 2-halogen-1,3-dicarbonylcompounds instead of the methylene compound. The halogen compoundsobtained can be reacted with an alkali metal cyanide, azide or nitrateto give the appropriate cyano, azido or nitro compounds (compare saidU.S. patent application Ser. No. 762,155).

For both of the process variants (a) and (b), Polar inert organicsolvents can be used as diluents. These include, in particular,nitriles, such as acetonitrile; ketones, such as acetone; formamides,such as dimethyl formamide, and ethers, such as diethyl ether,tetrahydrofuran and dioxan; and the like.

When carrying out the process variant (b), an acid binding agent isadded. Suitable for this purpose are tertiary amines, such astriethylamine, dimethylaniline and pyridine, as well as alkali metal oralkaline earth metal carbonates, oxides and hydroxides, such as sodiumcarbonate and sodium hydroxide; and the like.

The reaction temperatures in both process variants range, in general, atfrom substantially between about 10100 0., preferably from between about20-150 C.

When carrying out the reaction according to both of variants (a) and(b), the starting materials are preferably used in equimolarproportions, the carboxylic acid chlorides (III) possibly being in aslight excess. The reaction is, in general, complete after about 3-8hours. The chloride salt formed in the reaction, for example alkalimetal chloride or amine hydrochloride, is filtered on and the compoundof the Formula I is obtained directly by concentration of the reactionsolution or by recrystallization of the residue remaining after thesolvent has been distilled off.

Advantageously, the active compounds according to the present inventionexhibit strong insecticidal and acaricidal effects, with e.g.,comparatively low mammalian toxicity and concomitantly lowphytotoxicity. The instant active compounds can therefore be used withmarkedly good results for the control of noxious sucking and bitinginsects, Diptera and mites (Acarina) To the sucking insects contemplatedherein there belong, in the main, aphids, such as the green peach aphid(Myzus persicae), and the bean aphid (Doralis fabae); scales, such asAspidiotus hederae, Lecanium hesperidzun, and Pseudococcus marilimus;Thysanoptera, such as Hel'cinothrips femoralis; and bugs, such as thebeet bug (Piesma i fiadrata) and the bed bug (Climex lecrularius); andthe With the biting insects contemplated herein, there are classed, inthe main, butterfly caterpillars, such as Plutella maculipennis, andLymantria dispar; beetles, such as granary weevils (Sitophilusgranarius), the Colorado beetle (Leptz'notarsa decemlineata), and alsospecies living in the soil, such as the wireworms (Agriotes sp.) andlavrae of the cockchafer (Melolontha melolontha); cockroaches, such asthe German cockroach (Blattella germanica); Orthiptera, such as thehouse cricket (Gryllus domesticus); termites, such as Reticulitermes;Hymenoptera, such as ants; and the like.

The Diptera contemplated herein comprise, in particular, the flies, suchas the vinegar fly (Drosophila melanogaszer), the Mediterranean fruitfly (Ceratitis capitata), the house fiy (Musca domestica), andmosquitoes, such as the yellow fever mosquito (Aedes Aegypti); and thelike.

In the case of the mites contemplated herein, particularly important arethe spider mites (Tetranychidae) such as the two-spotted spider mite(Tetranychus urticae), and the European red mite (Paratetranychuspilosus); gall mites, such as the currant gall mite (Eriophyes ribis)and tarsonemids, such as T arsz'nemus pallidus, and ticks; and the like.

The pesticidal effects of the instant active compounds set in rapidlyand are long-lasting.

It will be appreciated that if the phenylhydrazones according to thepresent invention are used in the form of their salts, theireffectiveness, in general, changes only extremely slightly.

The instant active compounds also exhibit a certain fungicidal activity,particularly against phytopathogenic fungi, and a general microbicidalactivity, for example against fungi and bacteria, and may thus play asignificant part in industrial disinfection and preservation endeavors.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)diluents or extenders, e.g. those intended for conventional pesticadformulations, i.e. conventional pesticidal dispersible carrier vehiclessuch as solutions, emulsions, suspensions, emulsifiable concentrates,spray powders, pastes, soluble powders, dusting agents, granules, etc.These are prepared in known manner, for instance by extending the activecompounds with conventional pesticidal dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticidal surface-activeagents, including emulsifying agents and/ or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: inert dispersible liquid diluent carriers, including inertorganic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene,xylene, etc.), halogenated, especially chlorinated, aromatichydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleumfractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride,etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.),amines (e.g. ethanolamine, etc.) ethers, etheralcohols (e.g. glycolmonomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.),sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.)and/ or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, alumina,silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed sllicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and/ or anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfonates, aryl sulfonates, etc., and especially alkylarylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ordispersing agents, such as lignin, sulfite waste liquors, methylcellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/ or with such solid and/ or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other acaricides andinsecticides, or fungicides, herbicides, bactericides, etc., if desired,or in the form of particular dosage preparations for specificapplication made therefrom, such as solutions,

emulsions, suspensions, powders, pastes, and granules which are thusready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.195% by Weight, andpreferably 0.5% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or held application generallycontemplates those in which the active compound is present in an amountsubstantially between about 0.001-5 preferably 0.002-1%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprise mixtures of a conventional dispersiblecarrier vehicle such as (l) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/ or Water preferably including a surface-active etfectiveamount of a carrier vehicle assistant, e.g. a surface-active agent, suchas an emulsifying agent and/ or a dispersing agent, and an amount of theactive compound which is effective for the purpose in question and whichis generally between about 0.001%, and preferably 0.00295%, by weight ofthe mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment in finelydivided form, eg average particle diameter of from 50- microns, or evenless, i.e. mist form, for example by airplane crop spraying techniques.Only up to at most about a few liters/ hectare are needed, and oftenamounts only up to about 1 quart/acre, preferably 2-16 fluidounces/acre, are suflicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of activecompound or even the 100% active substance alone, eg about 20l00% byweight of the active compound.

In particular, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. arthropods, i.e. insectsand acarids, and more particularly, methods of combating at least one ofinsects and acarids which comprise applying to at least one ofcorrespondingly (a) such insects, (b) such acarids, and (c) thecorresponding habitat, i.e. the locus to be protected, a correspondinglycombative or toxic amount, i.e. an arthropodicidally, especiallyinsecticidally or acaricidally, eflective amount of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, pouring,fumigating, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

7 The unexpected superiority and outstanding activity of the particularnew compounds of the present invention is illustrated without limitationby the following examples:

EXAMPLE 1 Phaedon larvae test Solvent: 3 parts by weight dimethylformamide Emulsifier: 1 part by weight alkylaryl polyglycol ether Toproduce a suitable preparation of the particular active compound, 1 partby weight of such active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier, and the resultingconcentrate is diluted with water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the prepartion ofthe given active compound until dripping wet and then infested withmustard bettle larvae (Plzaedolz cochleariae) After the specified periodof time, the degree of destruction is determined as a percentage: 100%means that all the bettle larvae are killed, whereas means that none ofthe bettle larvae are killed.

The particular active compounds tested, their concentrations, theevaluation time, and the results obtained can be seen from the followingTable 1:

TABLE 1 (Plant-damaging insects) Phaedou larvae Concentration of Degreeof active destruction compound in percent Active compound number (seeTable 4) in percent after 3 days (A) 01 0.2 100 C N O. 02 0 NHN O C N Cl(known) EXAMPLE 2 Plutella test Solvent: 3 parts by weight dimethylformamide Emulsifier: 1 part by weight alkylaryl polyglycol ether Toproduce a suitable preparation of the particular active compound, 1 partby weight of such active compound is mixed with the stated amount ofsolvent containing the stated amount of emulsifier, and the resultingconcentrate is diluted with water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe given active compound until dew moist and are then infested withcaterpillars of the diamond-back moth (Pluzella maculipemzz's).

After the specified period of time, the degree of destruction isdetermined as a percentage: 100% means that all the caterpillars arekilled, Whereas 0% means that none of the caterpillars are killed.

The particular active compounds tested, their concentrations, theevaluation time and the results obtained can be seen from the followingTable 2:

TABLE 2 (Plant-damaging mites) Plutella Tetranychus test Solvent: 3parts by weight dimethyl formamide Emulsifier: 1 part by weightalkylaryl polyglycol ether To produce a suitable preparation of theparticular active compounds, 1 part by weight of such active compound ismixed with the stated amount of solvent containing the stated amount ofemulsifier, and the resulting concentrate is diluted with water to thedesired final concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately1030 cm., are sprayed with the preparation of the given active compounduntil dripping wet. These bean plants are heavily infested with spidermites (Tetranychus urticae) in all stages of development.

After the specified period of time, the effectiveness of the givenpreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:means that all the spider mites are killed, whereas 0% means that noneof the spider mites are killed.

The particular active compounds tested, their concentrations, theevaluataion time and the results obtained can be seen from the followingTable 3:

TABLE 3 (Plant-damaging mites) Tetnmychns urticac The following furtherexamples are set forth to illustrate, without limitation, the processfor producing the instant active compounds according to the presentinvention.

2-(3,5' bis-trifiuoromethyl-phenyl)-hydrazone, as colorless crystals ofM.P. 125 C. are obtained.

(ii) The potassium salt used as starting material can be prepared forexample as follows:

EXAMPLE 4 5 1 mol of the corresponding hydrazone is dissolved in Fethanol at C., and 1 11101 of ethanolic solution of po- I C tassiumhydroxide is added. After a short time, the potassium salt isprecipitated. After cooling, suction filtration I is eifeeted, followedby washing with ether and dryin l C CO2CH3 o 1 y 10 at -100 C. in avacuum.

0 1115 (iii) A further method of preparation of the starting material iscarried out as follows:

(i) 18,8 g, (0,05 ol) f dry potassium alt f cyano- The correspondinghydrazone is dissolved at 60 C. incarbomethoxy-carbonyl-(3,5-bis-trifluoromethyl phenyl)- benzene ortoluene, one equivalent of sodlum methylate or hydrazone are suspendedin 200 ml. of dry acetonitrile, 15 another sodium alcoholate is added,and the methanol and a solution of 6 g. (0.05 mol) propionyl chloride informed is then distilled off. The remainder of the solvent 50 ml.acetonitrile is added dropwise, with stirring. Stiris subsequentlyremoved or the benzene solution or susring is then effected for 4 hoursat 50 C. The suspension pension of the salt is used directly for furtherreaction. is concentrated in a vacuum, and the residue is recrystal- Ina manner analogous with that described in Example lized from 200 ml.ligroin. 15.5 g. (78% of the theory), 20 4, the following compoundsaccording to Formula I ofl-(a-cyano-acarbomethoxy)-carbonyl-Z-ethylcarbonylabove are alsoprepared:

Number Z X Y A M.P., C-

(22) 3,5-CF3 CN OCH: Q 160 (32) 3,5-012 CN 00113 0112 134 (73) 3,5-OF5CN 0011a 11-02112 93 (101) 201, 501 3 CN 00113 Q 144 CN OCH: 02115 101ON OCH: CH3 121 ON OCH: Q 162 ON OCHa C2H5 159 ON 0011a 0115 143 ON o0H311-0 112 122 UN 0CH3 11-C3H1 98 CN 002119 02115 1311 CN 002112 011201145-148 ON 002119 CH5 165-168 0N t-C4H9 0112 120-128 CN t-C4Hn C2115112-118 0N 502112 011:0(01191 155 UN OCHs CH3 150 0N 00113 011(01102 122ON 00113 011201 148 ON 00113 011201 149-150 0N 0011 0112011201 115-1180N 00112 01120112011201 GN 00113 011(01192 -117 CN OCH; CIII CHz 131-133(27 3,5-CF3 CN OCH3 CHC12 115 (281) 3,5-013 0N 00111 CH2CHCH1 109 (302)2,4,5-012 CN 00113 -CH:OH2 128 311) 2,4,5-013 0N 00112 -0112orr2o1 136321)... 2,4,5-013 0N 00112 -CH2CH2-CH2C1 94-90 (331) 2,4,5-012 0N OCH;011 01102 136-138 341) 2,4,5-012 0N 00111 OH2CH-OH 129 It will berealized that all of the foregoing compounds contemplated by the presentinvention possess the desired selective pesticidal, especiallyarthropodicidal, i.e. insecticidal or acaricidal, properties forcombating insects and acarids, and that such compounds have not only avery slight toxicity toward warm-blooded creatures, but also aconcomitantly low phytotoxicity.

As may be used herein, the terms arthropod, arthropodicidal andarthropodicide contemplate specifically both insects and acarids. Thus,the insects and acarids may be considered herein collectively asarthropods to be combated in accordance with the invention, andaccordingly the insecticidal and/ or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used will be an arthropodicidally effective amount which ineffect means an insecticidally or acaricidally effective amount of theactive compound for the desired purposes.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. N acyl 1,2 dicarbonyl-phenyl-hydrazone of the formula in which X iscyano, Y is selected from the group consisting of alkyl of 1-4 carbonatoms and alkoxy of 14 carbon atoms, In is a whole integer from 1 to 3,Z, each individually, is selected from the group consisting of chloroand trifluoromethyl, and A is selected from the group consisting ofalkyl of 1-4 carbon atoms, chloro-substituted alkyl of l4 carbon atoms,alkenyl of 3-4 carbon atoms, and phenyl.

2. Compound according to claim 1 wherein X is cyano, Y is C alkoxy, m is2-3, Z, each individually, is selected from the group consisting ofchloro and trifluoromethyl, and A is selected from the group consistingof C alkyl and phenyl.

3. Compound according to claim 1 wherein X is cyano, Y is C alkoxy, Ztaken together with the corresponding phenyl ring is selected from thegroup consisting of 3,S-bis-trifiuoromethyl-phenyl,2,4,5-trichloro-phenyl, 2- chloro-S-trifluoromethyl-phenyl and2-trifluoromethyl-4- chloro-phenyl, and A is selected from the groupconsisting of C alkyl and phenyl.

4. Compound according to claim 1 wherein such compound isa-cyano-u-carbomethoxy-carbonyl-N-ethylcarbonyl-3,5-bis-trifiuoromethyl-phenyl-hydrazoneof the formula (B o 01-1 a pound isa-cyano-u-carbomethoxy-carbonyl-N-acetyl-3,5-bis-trifluoromethyl-phenyl-hydrazone of the formula I /CN CH COOCH a y)a a 7. Compound according to claim 1 wherein such compound isa-cyano-a-carbomethoxy-carbonyl-N-acetyl=2,4,5'-trichloro-phenyl-hydrazone of the formula COOCH;

8. Compound according to claim 1 wherein such compound isa-cyano-a-carbomethoXy-carbonyl-N-ethylcarbonyl-2',4,5-trichloro-phenyl-hydrazoneof the formula 9. Compound according to claim 1 wherein such compound isa-cyano-ot-carbomethoxy-carbonyl-N-(n-propylcarbonyl) 3',5' bistrifluoromethyl-phenyl-hydrazone of the formula COOCIIg 10. Compoundaccording to claim 1 wherein such compound isa-cyano-a-carbomethoxy-carbonyl-N-ethylcarbonyl-2-chloro-5-trifluoromethyl-phenyl-hydrazoneof the formula I ON C-C H COOCH 6 I z s 3 References Cited UNITED STATESPATENTS 3,150,151 9/1964 Urbschat et al. 260465 X CHARLES B. PARKER,Primary Examiner D. H. TORRENOE, Assistant 'Examiner US. Cl. X.R.260193; 424304

